Patterning process of a semiconductor structure with a middle layer

ABSTRACT

A lithography method is provided in accordance with some embodiments. The lithography method includes forming a metal-containing layer on a substrate, the metal-containing layer including a plurality of conjugates of metal-hydroxyl groups; treating the metal-containing layer at temperature that is lower than about 300° C. thereby causing a condensation reaction involving the plurality of conjugates of metal-hydroxyl groups; forming a patterned photosensitive layer on the treated metal-containing layer; and developing the patterned photosensitive layer so as to allow at least about 6% decrease of optimum exposure (E op ).

PRIORITY DATA

The present application is a continuation application of U.S. patentapplication Ser. No. 14/868,043, filed Sep. 28, 2015, which isincorporated by reference herein in its entirety.

BACKGROUND

In integrated circuit (IC) fabrications, a patterned photoresist layeris used to transfer a designed pattern having small feature sizes from aphotomask to a wafer. The photoresist is light-sensitive and can bepatterned by a photolithography process. Furthermore, the photoresistlayer provides resistance to etch or ion implantation, which furtherrequires a sufficient thickness. When IC technologies are continuallyprogressing to smaller feature sizes, for example, down to 32nanometers, 28 nanometers, 20 nanometers and below, the thickness is notscaled down accordingly because of the resistance requirement. Depth offocus sufficient enough to cover the thicker photoresist degrades theimaging resolution. Multiple-film photoresist is introduced to overcomethe above challenge. However, while a variety of such multiple-filmphotoresists have been generally adequate for their intended purposes,they have not been entirely satisfactory in every aspect.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 illustrates a method for fabricating a semiconductor device usinga trilayer photoresist in accordance with various embodiments.

FIGS. 2A through 2G illustrate sectional views of one exemplarysemiconductor structure at various fabrication stages, constructed inaccordance with some embodiments.

FIG. 3 illustrates an example of a chemical reaction of a treatment to ahardmask, constructed according to aspects of the present disclosure insome embodiments.

FIG. 4 illustrates an example of a chemical reaction of a treatment to ahardmask, constructed according to aspects of the present disclosure insome embodiments.

DETAILED DESCRIPTION

It is understood that the following disclosure provides many differentembodiments, or examples, for implementing different features of variousembodiments. Specific examples of components and arrangements aredescribed below to simplify the present disclosure. These are, ofcourse, merely examples and are not intended to be limiting. Forexample, the formation of a first feature over or on a second feature inthe description that follows may include embodiments in which the firstand second features are formed in direct contact, and may also includeembodiments in which additional features may be formed interposing thefirst and second features, such that the first and second features maynot be in direct contact. In addition, the present disclosure may repeatreference numerals and/or letters in the various examples. Thisrepetition is for the purpose of simplicity and clarity and does not initself dictate a relationship between the various embodiments and/orconfigurations discussed.

As lithographic features are reduced, for example, to below 40nanometers (nm), high numerical aperture processes are needed toovercome the resolution limit. The use of a multiple-film photoresist(e.g., trilayer photoresist stack) appears to be promising in thisregard. Specifically, trilayer photoresist stack may provide forimprovements in pattern transfer, line edge roughness (LER), and linewidth roughness (LWR) among other benefits. In general, such a trilayerphotoresist stack includes an under layer, a middle layer over the underlayer, and a photoresist layer over the middle layer. Conventionally,the under layer and/or the middle layer of the trilayer stack maycontain silicon. The silicon-containing under layer and/or middle layerhave demonstrated good reflectivity control and reasonable etchselectivity. Moreover, for a trilayer photoresist stack to be used in anextreme ultraviolet lithography (EUVL), a metal-containing middle layermay be used. Such a metal-containing middle layer (e.g., a hardmasklayer) absorbs EUV wavelengths, so that using the metal-containinghardmask layer may provide increased sensitivity of a EUV photoresistthat is formed over the metal-containing middle layer. However, avariety of issues may occur especially at the interface of themetal-containing middle layer and the EUV photoresist such as forexample, one or more conjugates of metal-hydroxyl groups formed on thesurface of the metal-containing hardmask layer (i.e., the interfacebetween the EUV photoresist and the hardmask layer). Usually, suchconjugates of metal-hydroxyl groups formed at the interface may in turnresult in undesirably formed pattern of the photoresist (e.g., anundercut profile and/or a footing profile of the photoresist). Thus, thepresent disclosure provides methods to treat such metal-containinghardmask layers thereby providing an improved interface between ahardmask layer and an overlaying photoresist.

FIG. 1 is a flow chart of a method 100 of patterning a substrate (e.g.,a semiconductor wafer) according to various aspects of the presentdisclosure. The method 100 may be implemented, in whole or in part, by asystem employing deep ultraviolet (DUV) lithography, extreme ultraviolet(EUV) lithography, electron beam (e-beam) lithography, x-raylithography, and/or other lithography processes to improve patterndimension accuracy. In the present embodiment, EUV and/or e-beamlithography is used as the primary example. Additional operations can beprovided before, during, and after the method 100, and some operationsdescribed can be replaced, eliminated, or moved around for additionalembodiments of the method.

The method 100 is described below in conjunction with FIGS. 2A, 2B, 2C,2D, 2E, 2F, 2G wherein a semiconductor device 200 is fabricated by usingembodiments of the method 100. The semiconductor device 200 may be anintermediate device fabricated during processing of an IC, or a portionthereof, that may comprise SRAM and/or other logic circuits, passivecomponents such as resistors, capacitors, and inductors, and activecomponents such as p-type FETs (PFETs), n-type FETs (NFETs), fin-likeFETs (FinFETs), other three-dimensional (3D) FETs, metal-oxidesemiconductor field effect transistors (MOSFET), complementarymetal-oxide semiconductor (CMOS) transistors, bipolar transistors, highvoltage transistors, high frequency transistors, other memory cells,and/or combinations thereof.

Referring now to FIG. 1 in conjunction with FIG. 2A, the method 100begins with operation 102 in which a substrate 202 of a semiconductordevice 200 is provided. The semiconductor device 200 is a semiconductorwafer in the present embodiment. The semiconductor device 200 includes asemiconductor substrate 202, such as a silicon substrate in someembodiments. The substrate 202 may include another elementarysemiconductor, such as germanium, or diamond in some embodiments. Thesubstrate 202 may include a compound semiconductor, such as siliconcarbide, gallium arsenic, indium arsenide, and indium phosphide. Thesubstrate 202 may include an alloy semiconductor, such as silicongermanium, silicon germanium carbide, gallium arsenic phosphide, andgallium indium phosphide. The substrate 202 may include one or moreepitaxial semiconductor layer, such as semiconductor layer(s)epitaxially grown on a silicon substrate. For example, the substrate mayhave an epitaxial layer overlying a bulk semiconductor. Further, thesubstrate may be strained for performance enhancement. For example, theepitaxial layer may include semiconductor materials different from thoseof the bulk semiconductor such as a layer of silicon germanium overlyinga bulk silicon, or a layer of silicon overlying a bulk silicon germaniumformed by a process including selective epitaxial growth (SEG).Furthermore, the substrate 202 may include a semiconductor-on-insulator(SOI) structure. For examples, the substrate may include a buried oxide(BOX) layer formed by a process such as separation by implanted oxygen(SIMOX). In other embodiments, the substrate 202 may include a glasssuch as in thin film transistor (TFT) technologies.

Referring to FIG. 2B, method 100 proceeds to operation 104 with formingan underlayer (or material layer) 204 over the substrate 202. Thesemiconductor device 200 may also include other material layers andother circuit patterns. For example, the semiconductor device 200 mayinclude various doped features, such as doped well structure (e.g., aP-typed doped well and an N-type doped well) formed in the semiconductorsubstrate 202. In other embodiments, the semiconductor device 200 mayfurther include one or more material layers to be patterned (by etchingto remove or ion implantation to introduce dopants), such as adielectric layer to be patterned to form trenches for conductive linesor holes for contacts or vias; a gate material stack to be patterned toform gates; and/or a semiconductor material to be patterned to formisolation trenches. In other embodiments, multiple semiconductormaterial layers, such as gallium arsenic (GaAs) and aluminum galliumarsenic (AlGaAs), are epitaxially grown on the semiconductor substrateand are patterned to form various devices, such as light-emitting diodes(LEDs). In some other embodiments, the semiconductor device 200 includesfin active regions and three dimensional fin field-effect transistors(FinFETs) formed or to be formed thereon. The underlayer 204 isconfigured to provide resistance to etching or ion implantation. Theunderlayer 204 functions as a mask to protect the substrate 202 frometching or ion implantation. Accordingly, the underlayer 202 has asufficient thickness in this regard. In some embodiments, the underlayer202 includes an organic polymer free of silicon. In some embodiments,the forming the under layer 202 (i.e., operation 104) includes spin-oncoating and curing (such as a thermal baking process with a properbaking temperature).

Referring to FIG. 2C, method 100 then continues to operation 106 withforming a hardmask layer 206 (or metal-containing layer) over theunderlayer 204. Hardmask layer 206 is a silicon-based andmetal-containing layer so as to provide etch selectivity from theunderlayer 204. Furthermore, hardmask layer 206 provides increasedsensitivity to EUV light to a overlaying photoresist layer. In someother embodiments, hardmask layer 206 is designed to function as abottom anti-reflective coating that reduces reflection during alithography exposure process, thereby increasing the imaging contrastand enhancing the imaging resolution. In some alternative embodiments,hardmask layer 206 is formed over a underlayer 204 that is free ofsilicon (i.e. a silicon-free underlayer 202) to enhance etchingselectivity between the layers. In some embodiments, forming thehardmask layer 206 includes spin-on coating and curing (such as athermal baking process with a suitable baking temperature).

The present disclosure provides various embodiments of hardmask layer206. In an embodiment, hardmask layer 206 is a metal-containingsilicon-based hardmask. Such metal-containing silicon-based hardmask 206may be formed of any combination selected from a group consisting of: asilicon-containing polymer, a metalline polymer, an organic polymer, ametalorganic polymer, a crosslinker, a chromophore, a photo acidgenerator (PAG), a quencher, a fluoro additive, and a solvent. Examplesof the metal composition of the hardmask 206 may include Hf, Zr, Ti, Cr,W, Mo, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga,Tl, Ge, Sn, Pb, Sb, Ca, Ba, and/or Bi. In addition, the hardmask 206 mayfurther include a non-metallic catalyst and a metallic catalyst inaccordance with various embodiments. Regarding the catalysts, example ofthe metallic catalysts may include organometallic with organic ligands,metal oxide, metal nitride, and/or metal sulfide. Embodiments of thenon-metallic catalysts may include acids, bases, and ionic salts such asfor example, hydrogen chloride, sulfonic acid, acetic acid, amine,and/or ammonium salt. By including such catalysts in the formed hardmasklayer 206, a conjugation of metal-hydroxyl groups within and/or on asurface of the hardmask layer 206 may be reduced via a condensationreaction on the conjugation of metal-hydroxyl groups. Details of thecatalysts for reducing a conjugation of metal-hydroxyl groups isdiscussed below.

In another embodiment, the metal-containing silicon-based hardmask layer206 may further include additives such as capping agent(s) and/orchelating ligand(s). The additive may be blended with thesilicon-containing polymer, the metalline polymer, the organic polymer,and/or the metalorganic polymer that are used to form themetal-containing silicon-based hardmask 206. Such additives may beconfigured to passivate/cover free hydroxyl groups within and/or on thesurface of the hardmask layer 206 thereby reducing the conjugation ofmetal-hydroxyl groups within and/or on a surface of the hardmask layer206.

In accordance with an embodiment, the additive may include at least oneof the functional groups: alcohol, diol, thiol, dithiol,ethylenediaminetetraacetic acid (EDTA), amine, phosphine, alkene,alkyne, —I, —Br, —Cl, —NH2, —COOH, —OH, —SH, —N3, —S(═O)—, imine, vinylether, acetal, hemiacetal, ester, aldehyde, ketone, amide, sulfone,acetic acid, cyanide, and/or allene. Some specific examples of thecapping agent may be represented as:

Similarly, some specific examples of the chelating ligand may berepresented as:

More specifically, the chelating ligand may be in a variety ofcompositions and/or forms such as for example, M-OR, M-OOCR, M-OC(═O)OR,M-Cl, M-Br, M-NR3, M-CN, M-SR, M-C(═O)R, M-N(R)—C(═O)R, M-CR═CRR, M-R,EDTA, a bidentate ligand, a tridentate ligand, a hexadentate ligand, apolydentate ligand, wherein M represents a metal atom coordinated withthe chelating ligand.

The method 100 proceeds to operation 108 with treating (207 in FIG. 2D)the metal-containing silicon-based hardmask layer 206 so as to form atreated hardmask layer 206′ in accordance with various embodiments. Avariety of approaches may be used to treat the hardmask 206. In anembodiment, treating the hardmask 206 may include baking thesemiconductor device 200 in temperature ranging from about 100° C. toabout 300° C. In the example in which the hardmask 206 includes themetallic and/or the non-metallic catalysts, after the treating (i.e.,operation 108 in FIGS. 1 and 207 in FIG. 2D), the catalyst may induce acondensation reaction on at least two conjugates of the metal-hydroxylgroups within or on the surface of the hardmask 206. On the other hand,in the example in which the additive (e.g., the capping agent and/or thechelating ligand) is blended into the composition to form the hardmask206, a variety of chemical reactions (e.g., a replacement reaction, acondensation reaction, a S_(N)2 reaction, a S_(N)1 reaction, an E1reaction, an E2 reaction, an oxidation reaction, a reduction reaction, acycloaddition reaction, an elimination reaction, and a crosslinkingreaction) may occur on the conjugates of the metal-hydroxyl groupswithin or on the surface of the hardmask 206. In a specific embodiment,the chemical reaction induced by the capping agent and/or the chelatingligand may include passivate/cover free hydroxyl groups on the surfaceof the hardmask 206. Moreover, the functional groups (e.g., alcohol,diol, thiol, dithiol, ethylenediaminetetraacetic acid (EDTA), amine,phosphine, alkene, alkyne, —I, —Br, —Cl, —NH2, —COOH, —OH, —SH, —N3,—S(═O)—, imine, vinyl ether, acetal, hemiacetal, ester, aldehyde,ketone, amide, sulfone, acetic acid, cyanide, ketene, isocyanate, andallene) of the capping agent and/or the chelating ligand may beconfigured to induce the above-mentioned chemical reactions.Alternatively or additionally, in another embodiment, treating thehardmask 206 may include forming a passivation layer 208 over thehardmask 206 (FIG. 2E). In a specific embodiment, the passivation layermay be a polymeric layer formed on the surface of the hardmask 206wherein the polymeric layer includes Polyhydroxystyrene (PHS),methacrylate, polyether, silicon-containing polymers, organic polymerscontaining aromatic rings, or a combination hereof. According to thecurrent embodiment, a thickness of the passivation layer 208 may be ⅙the thickness of the hardmask 206. Yet in another embodiment, thetreating the hardmask 206 may include modifying the surface of thehardmask 206 using a variety of compositions such as for example, HMDS,diols, alcohols, organometallic with organic ligands, metal oxide, metalnitride, and/or metal sulfide. Furthermore, such a variety ofcompositions may be applied to the surface of the hardmask 206 and abaking step may be followed so as to reduce free hydroxyl groups on thesurface of the hardmask 206.

Referring now to FIG. 3, an example of the condensation reaction inducedby the catalyst is illustrated. As shown in FIG. 3, two free hydroxylgroups 301 and 303 (“—OH”) are formed and bonded to the metal(s) (“M”)305 and 307 of the hardmask 206. After the treating step 207 (operation108), the catalyst 309 may induce a condensation reaction to remove thefree hydroxyl groups to form treated hardmask 206′. More specifically,the condensation reaction may include combining one hydroxide from oneof the free hydroxyl groups and one hydrogen from the other freehydroxyl group to form water 311.

Referring now to FIG. 4, an example of a reaction induced by the cappingagent 401 is illustrated. As shown in, the capping agent 401 isconfigured to react with each of the free hydroxyl groups 301 and 303 ofthe hardmask 206 so as to form a passivated/treated hardmask 206′ (i.e.,free of free hydroxyl groups as shown in FIG. 4).

Referring to FIG. 2F, method 100 proceeds to operation 110 with forminga material layer 210 over the treated hardmask 206′. In an embodiment,the material layer 210 is formed by spin-on coating a liquid polymericmaterial onto the treated hardmask 206′. In an embodiment, the materiallayer 210 is further treated with a soft baking process and a hardbaking process. In an embodiment, the material layer 210 is a radiationsensitive layer, such as a photoresist including an I-line resist, a DUVresist including a krypton fluoride (KrF) resist and argon fluoride(ArF) resist, a EUV resist, an electron beam (e-beam) resist, and an ionbeam resist. In the present embodiment, the material layer 210 is aresist sensitive to EUV radiation.

The method 100 proceeds to operation 112 by exposing the photoresist 210to a radiation beam 230 in a lithography system, as shown in FIG. 2F.The radiation beam may be an I-line (365 nm), a DUV radiation such asKrF excimer laser (248 nm) or ArF excimer laser (193 nm), a EUVradiation (e.g., 13.5 nm), an e-beam, an x-ray, an ion beam, and/orother suitable radiations. Operation 112 may be performed in air, in aliquid (immersion lithography), and/or in a vacuum (e.g., for EUVlithography and e-beam lithography). In an embodiment, the radiationbeam is patterned with a mask, such as a transmissive mask or areflective mask, which may include resolution enhancement techniquessuch as phase-shifting and/or optical proximity correction (OPC). Inanother embodiment, the radiation beam is directly modulated with apredefined pattern, such as an IC layout, without using a mask (masklesslithography). In the present embodiment, the radiation beam is a EUVradiation and the operation 112 is performed in a EUV lithographysystem, such as the EUV lithography system.

Still referring to operation 112, after the exposure, the operation 112may further include a treatment process. An example of such treatmentprocesses may include baking the substrate 202.

The method 100 then proceeds to operation 114 by developing the exposedphotoresist 210 in a developer as shown in FIG. 2G. In an embodiment,the developer may be a positive tone developer that dissolves andremoves exposed portions of the photoresist 210 or a negative tonedeveloper that selectively dissolves and removes the unexposed areas ofthe photoresist 210 as well as the under-exposed areas of thephotoresist 210, thereby forming a patterned photoresist 210′. In theexample as shown in FIG. 2G, the patterned photoresist 210′ arerepresented by two line patterns. However, the following discussion isequally applicable to resist patterns represented by trenches. By usingthe current embodiments of the hardmask layer 206, a variety ofimprovements of the developed photoresist 210 may be provided such as,for example, sensitivity of the photoresist 210, reflectivity of thephotoresist, and other characteristic of the photoresist 210 known inthe art. In an example, for the hardmask layer 206 that includesaluminum oxide (Al₂O₃), an optimum exposure (E_(op)) may be decreased toabout 11 mJ while an E_(op) of about 13 mJ may be required with aconventional hardmask layer. That is, about 15% decrease of E_(op) maybe provided. In another example in which the hardmask layer 206 includesgermanium (Ge), an optimum exposure (E_(op)) may be decreased to about16 mJ while an E_(op) of about 17 mJ may be required with a conventionalhardmask layer. That is, about 6% decrease of E_(op) may be provided.

The method 100 may proceed to forming a final pattern and/or an ICdevice on the substrate 202. For example, method 100 proceeds to one ormore further operations to etch the substrate 202 using the patternedphotoresist 210′ as an etch mask, thereby transferring the pattern fromthe patterned photoresist 210′ to the treated hardmask 206′, theunderlayer 204, and/or the substrate 202.

The present disclosure provides a lithography method for fabricating asemiconductor device. More specifically, the currently disclosed methodis directed to fabricating a semiconductor device using a multi-layerphotoresist stack (e.g., a trilayer photoresist stack). As mentionedabove, a conventional trilayer photoresist stack uses silicon-containingmiddle layer as a hardmask, and in a further embodiment of using atrilayer photoresist in a EUVL, a metal-containing silicon-basedhardmask is employed in order to enhance sensitivity of the trilayerphotoresist to EUV light. However, in such a trilayer photoresist stackwith a metal-containing silicon-based hardmask, issues such as interfacedegradation between a hardmask and a photoresist may arise.Conventionally, such issues may be resolved by baking thesubstrate/hardmask in temperature generally higher than about 400° C. Inturn, baking the substrate in such high temperature, other issues (e.g.,contamination) may arise. Thus, the present disclosure provides variousembodiments to provide an improved hardmask and/or a passivated surfaceof a hardmask of a multi-layer photoresist stack. As such, the interfacebetween a hardmask and a photoresist may not be subjected to theabove-mentioned issues. Moreover, by using the presently disclosedembodiments, high baking temperature that is conventionally required topassivate a hardmask surface is not needed. In accordance with thecurrent embodiments, baking the disclosed hardmask at temperaturebetween about 100° C. and about 300° C. may be sufficient to cause themetal-containing silicon-based hardmask to avoid the issue (e.g.,interface degradation between the hardmask and a coupled photoresist).As such, the coupled photoresist may be more sensitive to a radiationsource (e.g., EUV radiation source), which means that the coupledphotoresist may only require lower exposure energy (e.g., decrease ofoptimum exposure (E_(op))) to be patterned/developed. Accordingly, amore flexible lithography method may be provided.

A lithography method is provided in accordance with some embodiments.The lithography method includes forming a metal-containing layer on asubstrate, the metal-containing layer including a plurality ofconjugates of metal-hydroxyl groups; treating the metal-containing layerat temperature that is lower than about 300° C. thereby causing acondensation reaction involving the plurality of conjugates ofmetal-hydroxyl groups; forming a patterned photosensitive layer on thetreated metal-containing layer; and developing the patternedphotosensitive layer so as to allow at least about 6% decrease ofoptimum exposure (E_(op)).

A lithography method is provided in accordance with some embodiments.The lithography method includes forming a metal-containing layer havinga metal hydroxide group on a substrate, wherein the metal-containinglayer includes an additive, wherein the additive is selected from thegroup consisting of a capping agent and a chelating ligand; treating themetal-containing layer at temperature that is lower than about 300° C.thereby causing the additive to react with the metal-hydroxyl group;forming a patterned photosensitive layer on the treated metal-containinglayer; and developing the patterned photosensitive layer so as to allowat least about 6% decrease of optimum exposure (E_(op)).

A lithography method is provided in accordance with some embodiments.The lithography method includes forming an under layer on a substrate;forming a metal-containing middle layer on the under layer; treating themetal-containing middle layer at temperature that is lower than about300° C. thereby reducing at least, in part, a plurality of conjugates ofmetal-hydroxyl group on a surface of the metal-containing layer; forminga patterned photosensitive layer on the metal-containing middle layer;and developing the patterned photosensitive layer so as to allow atleast about 6% decrease of optimum exposure (E_(op)).

The foregoing has outlined features of several embodiments so that thoseskilled in the art may better understand the detailed description thatfollows. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method comprising: forming a metal-containinglayer on a substrate, the metal-containing layer including silicon and ametal-hydroxyl group, the metal-hydroxyl group including a metaldirectly bonded to oxygen and hydrogen directly bonded to the oxygen,the metal being different from silicon; treating the metal-containinglayer to cause a condensation reaction involving the metal-hydroxylgroup that debonds the hydrogen from the oxygen, wherein the treating ofthe metal-containing layer includes performing a baking process on themetal-containing layer; forming a photosensitive layer on the treatedmetal-containing layer; and developing the photosensitive layer to forma patterned photosensitive layer.
 2. The method of claim 1, wherein thebaking process includes baking the metal-containing layer at atemperature ranging from about 100° C. to about 300° C. during theentire baking process.
 3. The method of claim 1, further comprisingforming an organic polymer layer on the substrate, and wherein theforming of the metal-containing layer on the substrate includes formingthe metal-containing layer on the organic polymer layer.
 4. The methodof claim 3, wherein the organic polymer layer is free of silicon, andwherein the forming of the metal-containing layer on the organic polymerlayer includes forming the metal-containing layer directly on theorganic polymer layer such that the metal-containing layer interfaceswith the organic polymer layer.
 5. The method of claim 1, wherein themetal-containing layer includes a material selected from the groupconsisting of Hf, Zr, Ti, Cr, W, Mo, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt,Cu, Ag, Au, Zn, Cd, Al, Ga, Tl, Ge, Sn, Pb, Sb, Ca, Ba, and Bi.
 6. Themethod of claim 1, wherein the metal-containing layer includes either ametal catalyst or a non-metal catalyst.
 7. The method of claim 6,wherein the metal catalyst includes a material selected from the groupconsisting of an organometallic with organic ligands, a metal oxide, ametal nitride, and a metal sulfide, and wherein the non-metal catalystincludes a material selected from the group consisting of hydrogenchloride, sulfonic acid, acetic acid, amine, and ammonium salt.
 8. Amethod comprising: forming a metal-containing layer having ametal-hydroxyl group on a substrate, wherein the metal-containing layerincludes silicon and an additive, the metal-hydroxyl group including ametal directly bonded to oxygen and hydrogen directly bonded to theoxygen, the metal being different from silicon; treating themetal-containing layer to cause the additive to react with themetal-hydroxyl group to debond the hydrogen from the oxygen; forming aphotosensitive layer on the treated metal-containing layer.
 9. Themethod of claim 8, further comprising developing the photosensitivelayer to form a patterned photosensitive layer.
 10. The method of claim8, wherein the additive is a capping agent.
 11. The method of claim 10,wherein the additive is a chelating ligand.
 12. The method of claim 11,wherein the chelating ligand is selected from the group consisting of amonodentate ligand, a bidentate ligand, a tridentate ligand, ahexadentate ligand, and a polydentate ligand.
 13. The method of claim 8,wherein the additive includes a functional group selected from the groupconsisting of alcohol, diol, thiol, dithiol, ethylenediaminetetraaceticacid (EDTA), amine, phosphine, alkene, alkyne, —I, —Br, —Cl, —NH2,—COOH, —OH, —SH, —N3, —S(═O)—, imine, vinyl ether, acetal, hemiacetal,ester, aldehyde, ketone, amide, sulfone, acetic acid, cyanide, ketene,isocyanate, and allene.
 14. The method of claim 8, wherein the treatingof the metal-containing layer includes forming a passivation layerdirectly on the metal-containing layer.
 15. The method of claim 8,wherein the treating of the metal-containing layer includes performing athermal treatment process on the metal-containing layer.
 16. Alithography method, comprising: forming an organic polymer layer free ofsilicon on a substrate; forming a metal-containing layer on the organicpolymer layer, the metal-containing layer including silicon and a firstconcentration of metal-hydroxyl groups, wherein each metal hydroxylgroup includes a metal directly bonded to oxygen and hydrogen directlybonded to oxygen, the metal being different from silicon; treating themetal-containing layer to reduce the concentration of metal-hydroxylgroups in the metal-containing layer such that the treatedmetal-containing layer has a second concentration of the metal-hydroxylgroups that is less than the first concentration; and forming aphotosensitive layer on the treated metal-containing layer.
 17. Themethod of claim 16, further comprising developing the photosensitivelayer so as to allow at least about 6% decrease of optimum exposure(E_(op)).
 18. The method of claim 16, wherein the treating themetal-containing layer includes applying a material on a surface of themetal-containing layer, the material selected from the group consistingof HMDS, diols, alcohols, organometallic with organic ligands, metaloxide, metal nitride, and metal sulfide.
 19. The method of claim 18,wherein the treating of the metal-containing layer includes performing athermal treatment process on the metal-containing layer at temperatureat a temperature ranging from about 100° C. to about 300° C. during theentire thermal treatment process.
 20. The method of claim 16, whereinthe forming of the photosensitive layer on the treated metal-containinglayer includes forming the photosensitive layer directly on the treatedmetal-containing layer such that the photosensitive layer interfaceswith the treated metal-containing layer.